Solvent free aqueous polyurethane dispersions and adhesive films therefrom for stretch fabrics

ABSTRACT

Novel aqueous polyurethane dispersions and adhesive films formed therefrom are provided. The aqueous polyurethane dispersions are provided in solvent-free systems of a prepolymer comprising at least one polyether or polyester polyol, a mixture of MDI isomers, and a diol. The adhesive films from such dispersions can be heat-activated for bonding, lamination, and adhesion of textile fabrics, including stretch fabrics.

FIELD OF THE INVENTION

The present invention relates to novel aqueous polyurethane dispersionsand adhesive films therefrom. Specifically, the present inventionrelates to solvent-free, stable dispersions, which comprise fully formedpolyurethaneurea with blocked isocyanate end groups. The dispersions canbe formed by prepolymer mixing processes. The present inventionadditionally relates to adhesive films, formed from such aqueousdispersions, which can be heat-activated for bonding, lamination andadhesion to textile fabrics. The films remain flexible and elastomericafter bonding, lamination or adhesion.

BACKGROUND OF THE INVENTION

Polyurethanes (including polyurethaneureas) can be used as adhesives forvarious substrates, including textile fabrics. Typically, suchpolyurethanes are either fully formed non-reactive polymers or reactiveisocyanate-terminated prepolymers. Such reactive polyurethane adhesivesoften require extended curing time to develop adequate bonding strength,which can be a disadvantage in manufacturing processes. In addition, theisocyanate groups of the polyurethanes are known to be sensitive tomoisture, which limits the storage stability and reduces the shelf lifeof the product incorporating such polyurethanes.

Typically, such polymers, when fully formed, are either dissolved in asolvent (solvent borne), dispersed in water (water borne), or processedas thermoplastic solid materials (hot melt) Notably, solvent-basedadhesives face ever-tightening health and environmental legislationaimed at reducing volatile organic compound (VOC) and hazardous airpollutant (HAP) emissions. Accordingly, alternatives to conventionalsolvent-based products are needed.

Hot-melt adhesives, although environmentally safe and easily applied asfilms, generally have high set and poor recovery when subject torepeated stretch cycles. Therefore, improvements are needed.

Many attempts have been made to develop water borne polyurethaneadhesives to overcome these deficiencies.

U.S. Pat. No. 5,270,433 discloses an “adhesive composition comprising asubstantially clear and solvent-free, aqueous, one-componentpolyurethane dispersion containing the reaction products of (a) a polyolmixture comprising polypropylene glycol, (b) a mixture of polyfunctionalisocyanates comprising α, α, α¹, α¹-tetramethyl xylene diisocyanate(TMXDI), (c) a functional component capable of salt formation in aqueoussolution, and (d) optionally, a chain-extending agent.” The adhesivefilms from this composition have low recovery power and poor heatresistance in view of the unsymmetrical structure and steric hindranceof isocyanate groups on TMXDI, preventing the formation of stronginter-chain urea hydrogen bonds in the hard segments of the polymer.

U.S. Patent Application Publication No. 2004/0014880 A1 discloses anaqueous polyurethane dispersion for adhesive bonding in wet and drylaminations stated to have superior coatability, adhesive strength andheat resistance. This dispersion contains a substantial amount oforganic solvent—methyl ethyl ketone (MEK).

U.S. Patent Application Publication No. 2003/0220463 A1 discloses amethod for making a polyurethane dispersion that is free of organicsolvent such as N-methylpyrrolidone (NMP). However, the composition islimited to a prepolymer having low free diisocyanate species, such asmethylene bis(4-phenylisocyanate) (4,4′-MDI). The process to producesuch a prepolymer with low free diisocyanate is complicated (asdisclosed in U.S. Pat. No. 5,703,193). Such processing also requiresshort path distillation of the free diisocyanate and is thus noteconomical in producing a prepolymer for making a polyurethanedispersion.

U.S. Pat. No. 4,387,181 discloses a stable aqueous polyurethanedispersion, containing N-methylpyrrolidone (NMP) solvent, prepared byreaction of carboxylic group-containing oxime-blocked,isocyanate-terminated prepolymer and polyamine. The prepolymer is madeby reaction of aromatic diisocyanates, such as4,4′-diphenylmethanediisocyanate (MDI) or toluene diisocyanate (TDI),with polyether or polyester polyols and a dihydroxy alkanoic acid. Theoxime-blocked isocyanate groups are capable of reacting with polyamineat 60 to 80° C. within 6 to 18 hours. The dispersion is stable instorage, and the film formed from the dispersion has good tensileproperties. However, this dispersion still has: organic solvent presentand the longer curing time needed is unsuitable for fabric bonding andlamination in practice.

U.S. Pat. No. 5,563,208 describes an acetone process to prepare anessentially solvent-free aqueous polyurethane dispersion, comprisingurethane prepolymers with blocked isocyanate groups and polyamineswithin the molecular weight range of 60 to 400 in a molar ratio ofblocked isocyanate groups to primary and/or secondary amino groups offrom 1:0.9 to 1:1.5. This dispersion is stable in storage at roomtemperatures and gives a heat-resistant binder in coating. It requireslong curing time (up to 30 minutes), which is still not suitable forfabric bonding and adhesion. Furthermore, the acetone process requiresan additional distillation step to remove the acetone from thedispersion, which makes this process less economical.

U.S. Pat. No. 6,586,523 describes an acetone process for preparing aself-crosslinking polyurethane dispersion for sizing agents, comprisinga prepolymer with isocyanate groups partially blocked and partiallyextended, and excess polyfunctional compounds having molecular weightsfrom 32 to 500 with primary or secondary amino and/or hydroxyl groups.This dispersion composition reduces the curing time to some degree, butstill has deficiencies because an additional distillation step to removethe acetone is required.

U.S. Pat. No. 6,555,613 describes a solvent-free aqueous dispersion of areactive polyurethane having a number average molecular weight (Mn) offrom 800 to 14,000, a degree of branching of from 0.0 to 3.0 mol/kg, andan isocyanate functionality from 2.0 to 6.0 per mole. The polyurethaneis made from a polyester polyol, a polyisocyanate and polyisocyanateadduct, with low molecular weight polyol and anion-forming units afterneutralizing incorporated in the polymer chains, and with blockedisocyanate groups capable of further reactions for crosslinking. Theresult of such dispersion is a coating material that is hard, glossy andelastic, but such coating material does not have the elastomericfeatures and stretch/recovery properties required for an adhesive to beused with stretch fabrics.

Thus, it would be desirable to provide an improved aqueous polyurethanedispersion, which overcomes one or more of the deficiencies of the priorart.

SUMMARY OF THE INVENTION

In a first aspect of the invention, a solvent-free aqueous polyurethanedispersion is formed as the reaction product of:

a) at least one polyether (including copolyethers) or polyester polyolcomponent having a number average molecular weight of about 600 to about3,500, preferably, a poly(tetramethylene ether) glycol having a numberaverage molecular weight of about 1,700 to about 2,100;

b) a polyisocyanate, which is a mixture of 4,4′- and 2,4′-methylenebis(phenyl isocyanate) (MDI) isomers, with the ratio of the 4,4′-MDI to2,4′-MDI isomers from about 65:35 to about 35:65; and

c) at least one diol compound with: (i) hydroxy groups capable ofreacting with the mixture of MDI isomers of component b) and (ii) atleast one carboxylic acid group capable of forming a salt uponneutralization, wherein the at least one carboxylic acid group isincapable of reacting with the mixture of MDI isomers of component b).

Components a), b), and c), make up a urethane prepolymer that can befurther combined with the following components to provide aqueouspolyurethane dispersions:

d) at least one neutralizing agent to form an ionic salt with thecomponent c);

e) at least one monofunctional dialkyl amine compound as a blockingagent for isocyanate groups;

f) optionally, at least one diamine chain extension component; and

g) optionally, at least one polymeric component having a molecularweight of greater than about 500, with at least three or more primaryand/or secondary amino groups per mole of the polymer.

The dispersion may include at least one surface active agent (alsoreferred to as dispersant or surfactant, ionic and/or non-ionic), atleast one antifoam and/or defoam agent and, preferably, at least onerheological modifier.

Other additives such as anti-oxidants, UV stabilizers, colorants and/orpigments may optionally be added to the aqueous dispersion before,during, or after the prepolymer is dispersed as the process allows.

When the aqueous dispersion is coated on a release paper and convertedto an adhesive film tape, the dialkylamine component e) is selected sothat (i) the blocked isocyanate groups are essentially stable in boththe coating and drying processes as well as in ambient storageconditions, while, concurrently, (ii) the adhesive film containing theblocked isocyanate groups is capable of being heat-activated attemperatures of about 100° C. to about 200° C., under pressure, forfabric bonding and lamination.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will be described in the following detaileddescription with reference to the following drawings:

FIG. 1 is a flowchart showing processing steps that may be used to applydispersions or films according to the invention using a spreadingmethod;

FIG. 2 is a flowchart showing processing steps that may be used to applydispersions or films according to the invention using a dipping method;

FIG. 3 is a flowchart showing processing steps that may be used to applydispersions or films according to the invention using a painting orspraying method;

FIG. 4 is a schematic diagram of a process using a flat bed laminationmachine to form a laminated article;

FIG. 5 is a cross-sectional view showing application of dispersions orfilms according to the invention onto substrates using a spreadingmethod;

FIG. 6 is a cross-sectional view showing application of dispersions orfilms according to the invention onto substrates using a dipping method;

FIG. 7 is a cross-sectional view showing application of dispersions orfilms according to the invention onto substrates using a painting orspraying method;

FIG. 8 is an illustration of a knife blade that can be used todistribute dispersions or films according to the invention;

FIG. 9 is an exploded view of a portion of the knife blade of FIG. 8;

FIG. 10 is a front view of a woman's brassiere incorporating dispersionsor films according to the invention;

FIG. 11 is a cross sectional view taken along line 11—11 of FIG. 10showing a brassiere cup;

FIG. 12 is a partial exploded, view taken from FIG. 11 showing thebrassiere cup and film interface at the peripheral region surroundingthe cup; and

FIG. 13 is a front view of a woman's panty incorporating dispersions orfilms according to the invention.

DETAILED DESCRIPTION OF THE INVENTION

Aqueous polyurethane dispersions falling within the scope of the presentinvention are provided from particular urethane prepolymers, which alsoform an aspect of the present invention.

Urethane prepolymers, or capped glycols, can generally be conceptualizedas the reaction product of a polyol, a polyisocyanate, and a compoundcapable of salt-forming upon neutralization, before the prepolymer isdispersed in water and is chain-extended. Such prepolymers can typicallybe made in one or more steps, with or without solvents. Depending onwhether the prepolymer is: dissolved in a less volatile solvent (such asMEK, or NMP) which will remain in the dispersion; dissolved in avolatile solvent such as acetone, which can be later removed; or isdispersed in water without any solvent; the dispersion process can beclassified in practice as the solvent process; acetone process, orprepolymer mixing process. The prepolymer mixing process hasenvironmental and economical advantages, and therefore is preferred asthe basic process for making the solvent-free aqueous dispersions, inthe present invention.

In the prepolymer mixing process, it is important that the viscosity ofthe prepolymer is adequately low enough, without dilution by a solvent,to be transported and dispersed in water. The present invention in oneembodiment, relates to polyurethane dispersions derived from such aprepolymer, which meet this viscosity requirement and do not have anyorganic solvent in the prepolymer or in the dispersion. In accordancewith the invention, the prepolymer is the reaction product of a polyola), a diisocyanate b) and a diol compound c).

The present invention can, in one embodiment, provide novel,solvent-free, stable, aqueous polyurethane dispersions, which can beprocessed and applied directly as adhesive materials (i.e., without theneed of any additional adhesive materials) for coating, bonding, andlamination of planar sheet articles including textile fabrics andnonwovens, by conventional techniques. Aqueous polyurethane dispersionsfalling within the scope of the present invention may be provided withessentially no emission of volatile organic materials; acceptable curingtime in production; and good adhesion strength, heat resistance, andstretch/recovery properties in finished products and in practicalapplications.

The present invention can, in an additional embodiment, provide adhesivefilms or tapes that can be coated on a release paper, whereby aqueousdispersions of the invention can be used for bonding and lamination ofplanar sheet articles including textile fabrics and nonwovens. Theadhesion can be activated, by applying heat and/or pressure onto asubstrate and the adhesive film, with a residence time of less than oneminute, such as from less than about one second to about five minutes,for example, from about 15 seconds to about 60 seconds. The thus bondedarticles have good stretch/recovery properties and are expected to bedurable in normal wear and wash cycles.

As used herein, the term “aqueous polyurethane dispersion” refers to acomposition containing at least a polyurethane or polyurethane ureapolymer or prepolymer (such as the polyurethane prepolymer describedherein) that has been dispersed in an aqueous medium, such as water,including de-ionized water. The term further relates to such acomposition that has been subjected to drying, for example, in theformation of an adhesive film or tape.

As used herein, the term “solvent,” unless otherwise indicated, refersto a non-aqueous medium, wherein the non-aqueous medium includes organicsolvents, including volatile organic solvents (such as acetone) andsomewhat less volatile organic solvents (such as MEK, or NMP).

As used herein, the term “essentially solvent-free” or “essentiallysolvent-free system” refers to a composition or dispersion wherein thebulk of the composition or dispersed components has not been dissolvedor dispersed in a solvent.

As used herein, the term “adhesive film or tape” refers to a layercomprising an aqueous polyurethane dispersion (such as the aqueouspolyurethane dispersion containing the polyurethane prepolymer describedherein) that can be directly applied to an article or release paper,which can be used for adhesion to form an elastic or stretch article.

As used herein, the term “stretch article” refers to an article, forexample a textile fabric, which has at least one elastic property, inpart, due to the application of an adhesive film or tape as describedherein.

Polyol components a), suitable as a starting material for preparingurethane prepolymers according to the invention, are polyether glycolsand polyester glycols of number average molecular weight of about 600 toabout 3,500. In accordance with the invention, polyether polyols are ofparticular advantage and are therefore used with preference.

Examples of polyether polyols that can be used include those glycolswith two or more hydroxy groups, from ring-opening polymerization and/orcopolymerization of ethyleneoxide, propylene oxide, trimethylene oxide,tetrahydrofuran, and 3-methyltetrahydrofuran, or from condensationpolymerization of a polyhydric alcohol, preferably a diol or diolmixtures, with less than 12 carbon atoms in each molecule, such asethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol,1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and1,12-dodecanediol. A linear, bifunctional polyether polyol is preferred,and a poly(tetramethylene ether) glycol of molecular weight of about1,700 to about 2,100, such as Terathane® 1800 (Invista) with afunctionality of 2, is particularly preferred in the present invention.

Examples of polyester polyols that can be used include those esterglycols with two or more hydroxy groups, produced by condensationpolymerization of aliphatic polycarboxylic acids and polyols, or theirmixtures, of low molecular weights with no-more than 12 carbon atoms ineach molecule. Examples of suitable polycarboxylic acids are malonicacid, succinic acid, glutaric acid, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, undecanedicarboxylic acid anddodecanedicarboxylic acid. Example of suitable polyols for preparing thepolyester polyols are ethylene glycol, 1,3-propanediol, 1,4-butanediol,1,5-pentanediol 1,6-hexanediol, neopentyl glycol,3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol,1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol. A linear,bifunctional polyester polyol with a melting temperature of about 5° C.to about 50° C. is preferred.

The polyisocyanate component b), suitable as another starting materialfor making urethane prepolymers according to the invention, is an isomermixture of diphenylmethane diisocyanate (MDI) containing 4,4′-methylenebis(phenyl isocyanate) and 2,4′-methylene bis(phenyl isocyanate) in therange of 4,4′-MDI to 2,4′-MDI isomer ratios of between about 65:35 toabout 35:65, preferably in the range of about 55:45 to about 45:55 andmore preferably at about 50:50. Examples of suitable polyisocyanatecomponents include Mondur® ML (Bayer), Lupranate® MI (BASF), andIsonate® 50 O,P′ (Dow Chemical).

Diol compounds c), suitable as further starting materials for preparingurethane prepolymers according to the invention, include at least onediol compound with: (i) two hydroxy groups capable of reacting with thepolyisocyanates b); and (ii) at least one carboxylic acid group capableof forming salt upon neutralization and incapable of reacting with thepolyisocyanates b). Typical examples of diol compounds c) having acarboxylic acid group, include 2,2-dimethylopropionic acid (DMPA),2,2-dimethylobutanoic acid, 2,2-dimethylovaleric acid, and DMPAinitiated caprolactones such as CAPA® HC 1060 (Solvay). DMPA ispreferred in the present invention.

The prepolymer can be prepared by mixing starting materials a), b), andc) together in one step and by reacting at temperatures of about 50° C.to about 100° C. for adequate time until all hydroxy groups areessentially consumed and a desired % NCO of the isocyanate group isachieved. Alternatively, this prepolymer can be made in two steps byfirst reacting starting material a) with excess b), followed by reactingwith component c) until a final desired % NCO of the prepolymer isachieved. For example, the % NCO may range from about 1.3 to about 6.5,such as from about 1.8 to about 2.6. Significantly, no organic solventis added to or mixed with the starting materials before, during or afterthe reaction.

In an embodiment of the present invention, the prepolymer comprisescomponents a), b), and c), which are combined together and provided inthe following ranges of weight percentages, based on the total weight ofthe prepolymer:

-   about 34% to about 89% of component a),-   about 59% to about 10% of component b); and-   about 7.0% to about 1.0% of component c).

In another embodiment of present invention, the prepolymer comprisesTerathane® 1800 polyether glycol as component a), Mondur® MLdiisocyanate as component b), and 2,2-dimethylopropionic acid (DMPA) ascomponent c). Within such embodiments, these components may, forexample, be present in the following ranges of weight percentages, basedon the total weight of the prepolymer:

-   a) Terathane® 1800 polyether glycol: about 61% to about 80%;-   b) Mondur® ML diisocyanate: about 35% to about 18%; and-   c) 2,2-dimethylopropionic acid (DMPA): about 4.0% to about 2.0%.

The prepolymer prepared from components a), b) and c) should have a bulkviscosity (without any solvent present) below about 6,000 poises, suchas below about 4,500 poises, measured by the falling ball method at 40°C. This prepolymer, containing carboxylic acid groups along the polymerchains, can be dispersed with a high speed disperser into a de-ionizedwater medium that comprises: at least one neutralizing agent d), to forman ionic salt with the acid; at least one surface active agent (ionicand/or non-ionic dispersant or surfactant); and, optionally, at leastone diamine chain extension component f). Alternatively, theneutralizing agent can be mixed with the prepolymer before beingdispersed into the water medium. At least one antifoam and/or defoamagent and preferably at least one rheological modifier can be added tothe water medium before, during, or after the prepolymer is dispersed.

Examples of suitable neutralizing agents d) to convert the acid groupsto salt groups include: tertiary amines (such as triethylamine,N,N-diethylmethylamine, N-methylmorpholine, N,N-diisopropylethylamine,and triethanolamine) and alkali metal hydroxides (such as lithium,sodium and potassium hydroxides). Primary and/or secondary amines may bealso used as the neutralizing agent for the acid groups. The degrees ofneutralization are generally between about 60% to about 140%, forexample, in the range of about 80% to about 120% of the acid groups.

Examples of suitable diamine chain extenders f) include:1,2-ethylenediamine, 1,4-butanediamine, 1,6-hexamethylenediamine,1,12-dodecanediamine, 1,2-propanediamine, 2-methyl-1,5-pentanediamine,1,2-cyclohexanediamine, 1,4-cyclohexanediamine,4,4′-methylene-bis(cyclohexylamine), isophorone diamine,2,2-dimethyl-1,3-propanediamine, meta-tetramethylxylenediamine, andJeffamine® (Texaco) of molecular weight less than 500.

Examples of suitable surface active agents include: anionic, cationic,or nonionic dispersants or surfactants, such as sodium dodecyl sulfate,sodium dodecylbenzenesulfonate, ethoxylated nonylphenols, and laurylpyridinium bromide.

Examples of suitable antifoaming or deforming agents include: Additive65 (a silicone additive from; Dow Corning), and Surfynol™ DF 110L (ahigh molecular weight acetylenic glycol non-ionic surfactant from AirProducts & Chemicals).

Examples of suitable rheological modifiers include:hydrophobically-modified ethoxylate urethanes (HEUR),hydrophobically-modified alkali swellable emulsions (HASE), andhydrophobically-modified hydroxy-ethyl cellulose (HMHEC).

At least one monofunctional dialkyl amine compound e), as the blockingagent for isocyanate; groups, is added to the water medium during orafter the prepolymer is dispersed. For example, the blocking agent canbe added to the water mixture immediately after the prepolymer isdispersed. Optionally at least one polymeric, component g) (MW>about500), with at least three or more primary and/or secondary amino groupsper mole of the polymer, is added to the water medium after theprepolymer is dispersed and the blocking agent is added.

Examples of suitable mono-functional dialkylamine blocking agents e)include: N,N-diethylamine, N-ethyl-N-propylamine, N,N-diisopropylamine,N-tert-butyl-N-methylamine, N-tert-butyl-N-benzylamine,N,N-dicyclohexylamine, N-ethyl-N-isopropylamine,N-tert-butyl-N-isopropylamine, N-isopropyl-N-cyclohexylamine,N-ethyl-N-cyclohexylamine, N,N-diethanolamine, and2,2,6,6-tetramethylpiperidine. The molar ratio of the amine blockingagent to the isocyanate groups of the prepolymer prior to dispersion inwater generally should range from about 0.05 to about 0.50, for examplefrom about 0.20 to about 0.40. Catalysts may be used for the de-blockingreactions.

Examples of the suitable polymeric component g) include:polyethylenimine, poly(vinylamine), poly(allylamine), andpoly(amidoamine) dendrimers.

Other additives that may be optionally included in the aqueousdispersion include: anti-oxidants, UV stabilizers, colorants, pigments,crosslinking agents, phase change materials (i.e., Outlast®,commercially available from Outlast Technologies, Boulder, Colo.),antimicrobials, minerals (i.e., copper), microencapsulated well-beingadditives (i.e., aloe vera, vitamin E gel, caffeine, scents or aromas),nanoparticles (i.e., silica or carbon), calcium carbonate, flameretardants, antitack additives, chlorine degradation additives, and/ordye-assist agent's (i.e., Methacrol®, commercially available from E.I.DuPont de Nemours, Wilmington, Del.). Such optional additives may beadded to the aqueous dispersion before, during, or after the prepolymeris dispersed, as the process allows. No organic solvent is added to theaqueous dispersion at any time.

Polyurethane aqueous dispersions falling within the scope of the presentinvention should be expected to have a solids content of from about 10%to about 50% by weight, for example from about 30% to about 45% byweight. The viscosity of polyurethane aqueous dispersions falling withinthe scope of the present invention may be varied in a broad range fromabout 10 centipoises to about 100,000 centipoises depending on theprocessing and application requirements. For example, in one embodiment,the viscosity is in the range of about 500 centipoises to about 30,000centipoises. The viscosity may be varied by using an appropriate amountof thickening agent, such as from about 0 to about 2.0 wt %, based onthe total weight of the aqueous dispersion.

The solvent-free aqueous polyurethane dispersions of the presentinvention are particularly suitable for adhesive films or tapes, whichcan be used for fabric bonding, lamination, and adhesion purposes whenapplied with heat and pressure for a relatively short period of time.Pressures, can for example, range from about atmospheric pressure toabout 60 psi and times can range from less than about one second toabout 30 minutes in accordance with the bonding method used.

Such adhesive films or tapes may be made by coating the dispersion ontoa release paper and drying to remove water at temperatures below about100° C. through commercially available processes to form a film on thepaper. The formed film sheets can be slit into strips of desired widthand wound-up into spools for later use in applications to form stretcharticles, for example textile fabrics. Examples of such applicationsinclude: stitch-less or seamless garment constructions; seam seal andreinforcement; labels and patches bonding to garments; and localizedstretch/recovery enhancement. The adhesion bonding can be developed inthe temperature range of from about 100° C. to about 200° C., such asfrom about 130° C. to about 200° C., for example, from about 140° C. toabout 180° C., in a period of seconds to minutes, for example, less thanabout one minute. This bonding is expected to be strong and durable whenexposed to repeated wear, wash, and stretch in a textile fabric garment.

In addition, articles with laminated films can be molded. For example,fabric can be molded under conditions appropriate for the hard yarn inthe fabric.

Lamination can be carried out to secure the film to a fabric using anymethod wherein heat is applied to the laminate surface. Methods of heatapplication include, for example, ultrasonic, direct heat, indirectheat, and microwave. Such direct lamination may provide an advantage inview of other methods used in the art in that the film may not only bondto the a substrate via a mechanical interaction but also via a chemicalbond. For example, if the substrate has any reactive hydrogen functionalgroups, such groups may react with the isocyanate and hydroxyl groups onthe film polymer, thereby providing a chemical bond between thesubstrate and the film polymer. Such chemical bonding can give a film amuch stronger bond to the substrate. Such bonding may occur in dry filmsthat are cured onto a substrate or in wet dispersions that are dried andcured in one step. Materials without an active hydrogen includepolypropylene fabrics and anything with a fluoropolymer or a siliconebased surface. Materials with an active hydrogen include, for example,nylon, cotton, polyester, wool, silk, cellulosics, acetates, metals, andacrylics.

Methods that can be used to apply dispersions and films falling withinthe scope of the present invention on an article include, but are notlimited to: roll coating (including reverse roll coating); use of ametal tool or knife blade (for example, pouring a dispersion onto asubstrate and then casting the dispersion into uniform thickness byspreading it across the substrate using a metal tool, such as a knifeblade); spraying (for example, using a pump spray bottle); dipping;painting; printing; stamping; and impregnating the article. Thesemethods can be used to apply the dispersion directly onto a substratewithout the need of further adhesive materials and can be repeated ifadditional/heavier layers are required. The dispersions can be appliedto any fabrics of knits, wovens or nonwovens made from synthetic,natural, or synthetic/natural blended materials for coating, bonding,lamination and adhesion purposes. The water in the dispersion can beeliminated with drying during the processing (for example, via airdrying or use of an oven), leaving the precipitated and coalescedpolyurethane layer on the fabrics to form an adhesive bond.

At least one coagulant may optionally be used to minimize penetration ofdispersions according to the invention into a fabric or other article.Examples of coagulants that may be used include calcium nitrate(including calcium nitrate tetrahydrate), calcium chloride, aluminumsulfate (hydrated), magnesium acetate, zinc chloride (hydrated) and zincnitrate.

An example of a tool that can be used for applying dispersions fallingwithin the scope of the present invention is the knife blade shown inFIGS. 8 and 9. The knife blade 100, can be made of metal or any othersuitable material. The knife blade can heave a gap of a predeterminedwidth 102 and thickness 104. The gap may range in thickness, forexample, from 5 mils to 50 mils, such as a thickness of 5 mils; 10 mils,15 mils, 25 mils, 30 mils, or 45 mils.

The thickness of dispersions and films-falling within the scope of thepresent invention may vary, depending on the application and method ofapplication. In the case of dry tapes, the final thickness may, forexample, range from about 0.1 mil to about 250 mil such as from about0.5 mil to about 25 mil, including from about 1 to about 6 mil (onemil=one one thousandth of an inch). For liquid dispersions, the amountused may, for example, range from about 2.5 g/m² to about 6.40 kg/m²,such as from about 12.7 to about 635 g/m², including from about 25.4 toabout 152.4 g/m².

Types of planar sheets and tapes that can be coated with dispersions andfilms falling within the scope of the present invention include, but arenot limited to: fabrics, including wovens and knits; nonwovens; leather(real or synthetic); paper; metal; plastic; and scrim.

End articles that can be produced using the dispersions and filmsfalling within the scope of the present invention include, but are notlimited to: apparel, which includes any type of garment or article ofclothing; knitted gloves; upholstery; hair accessories, bed sheets;carpet and carpet backing; conveyor belts; medical applications, such asstretch bandages; personal care items, including incontinence andfeminine hygiene products; and footwear.

Examples of apparel or garments that can be produced using thedispersions and films falling within the scope of the present invention,include but are not limited to, undergarments, brassieres, panties,lingerie, swimwear, shapers, camisoles, hosiery, sleepwear, aprons,wetsuits, ties, scrubs, space suits, uniforms, hats, garters,sweatbands, belts, active wear, outerwear, rainwear, cold-weatherjackets, pants, shirtings, dresses, blouses, mens and womens tops,sweaters, and all components therein.

FIG. 4 is a representative diagram of a flatbed laminating machine. Aroll of fabric substrate 72 is unwound and, preheated in zone 78. Asecond roll of fabric substrate 76 and roll of film 74 are unwound andenter the lamination heat/pressure zones 80. After heating, thefabric/film/fabric sandwich structure is cooled in the cooling zone 82.Roll 84 represents the rolled up fabric/film/fabric laminate.

Methods for performing and overcoming common problems in reverse rollcoating are described in Walter, et al., “Solving common coating flawsin Reverse Roll Coating,” AIMCAL Fall Technical Conference (Oct. 26–29,2003), the entire disclosure of which is incorporated herein byreference.

Dispersions and films falling within the scope of the present inventionmay be applied continuously or selectively to a given substrate. In thisregard, FIGS. 5–7 show, in cross-sectional view, schematic illustrationsof applications of dispersions and films falling within the scope of thepresent invention. In these figures, substrates are represented by thickblack lines and dispersions and films falling within the scope of thepresent invention are represented as: (1) two parallel thin lines whenapplied via a spreading method (via use of a knife blade, etc.), asshown in FIG. 5; (2) a zigzag line superimposed on a thick black linewhen applied via a dipping method, as shown in FIG. 6; or (3) a zigzagline between or above thick black lines when applied via a painting orspray method, as shown in FIG. 7. The drawings on the left-hand side ofthe figures, designated with a number followed by the letter “a”,represent continuous application of dispersions and films falling withinthe scope of the present invention whereas the drawings on theright-hand side of the figures, designated with a number followed by theletter “b,” represent selective or segmented application of dispersionsand films falling within the scope of the present invention. While notshown in FIGS. 5–7, it is also contemplated that dispersions and filmsfalling within the scope of the present invention can be applied bothcontinuously and in segments in the same application, for example,continuously on or between some layers, and in segments on or betweenother, layers.

FIGS. 10–13 show representative examples of garments that can be made toincorporate dispersions or films falling within the scope of the presentinvention.

FIG. 10 shows a brassiere 110 having fabric brassiere cups 112 formedwithin a support structure that includes a peripheral region 114surrounding the cups 112, and body-wrapping sides 116 that terminatewith fastening means, such as a hook 118 and mating loop 120. Thebrassiere 110 further includes shoulder straps 122. The brassiere 110can be made to incorporate dispersions or films falling within the scopeof the present invention. Such dispersions or films can be provided foror on any number of locations on the brassiere, including, but notlimited to, the shoulder straps 122, the peripheral region 114, and thebody-wrapping sides 116. Such dispersions or films can be providedanywhere where a seam would be expected to be present to join one ormore segments of material in the bra. As shown in FIG. 10, the brassierecups 112 and geometric shaped regions 124 along the body wrapping sides116 do not have film applied. All other fabric components include a filmaccording to the invention. While not specifically shown in FIG. 10,brassiere cups 112 may be molded using dispersions falling within thescope of the present invention.

FIG. 11 shows a cross-sectional view of a brassiere cup 112. FIG. 12shows an exploded view of the edge of the cup that meets the peripheralregion 114 surrounding the cup. As shown in FIGS. 11 and 12, thebrassiere cup 112 is formed of fabric to which no dispersion or film hasbeen applied. The peripheral region 114 has a film applied, and thus hasa greater thickness than the fabric of the cup, which comprises thethickness of the film and fabric together. The peripheral region 114offers some breast supporting rigidity and firmness, without theuncomfortable rigidity provided by an underwire.

FIG. 13 shows a woman's panty or brief 130 that can be made toincorporate dispersions or films falling within the scope of the presentinvention for enhanced elasticity or enhanced support. Such dispersionsor films can be provided for or on any number of locations on thepanties or briefs 130, including, but not limited to, the waistband 132and the leg openings 134.

Analytical Methods

In the examples that follow, the following analytical methods were used:

Peel Strength for Adhesive Bonds

ASTM D903-93, the entire disclosure of which is incorporated herein byreference, was modified for testing of film laminated fabrics. Thesample size used for testing was 2 inches×6 inches (5 cm×15 cm). Theseparation rate was 2 inches per minute (5 centimeter per minute). Dataare reported as pounds of force per inch of sample width (kilogram permillimeter), as shown in Table 2.

Wash Test

AATCC test method 150-2001, the entire disclosure of which isincorporated herein by reference, was used for the washing of molded bracups. The machine cycle was (I) normal/cotton sturdy. The washing tempwas (III) 41° C. The drying procedure was (A) (i) tumble cotton sturdy66° C. for 30 minutes with a 10 minute cool down time.

EXAMPLES

Representative embodiments of the present invention will be describedwith reference to the following examples that illustrate the principlesand practice of the present invention. In these examples:

the reference numbers refer to elements shown in the flowcharts of FIGS.1–3 and, where appropriate, the cross-sectional illustrations of FIGS.5–7;

Terathane® 1800 is a linear polytetramethylene ether glycol (PTMEG),with a number average molecular weight of 1,800 (commercially availablefrom Invista, S. à. r. L., of Wichita, Kans. and Wilmington, Del.);

Pluracol® HP 4000D is a linear, primary hydroxyl terminatedpolypropylene ether glycol, with a number average molecular weight of400 (commercially available from BASF, Bruxelles, Belgium);

Mondur® ML is an isomer mixture of diphenylmethane diisocyanate (MDI)containing 50–60% 2,4′-MDI isomer and 50–40% 4,4′-MDI isomer(commercially available from Bayer, Baytown, Tex.);

Lupranate® MI is an isomer mixture of diphenylmethane diisocyanate (MDI)containing 45–55% 2,4′-MDI isomer and 55–45% 4,4′-MDI isomer(commercially available from BASF, Wyandotte, Mich.);

Isonate® 125MDR is a pure mixture of diphenylmethane diisocyanate (MDI)containing 98% 4,4′-MDI isomer and 2% 2,4′-MDI isomer (commerciallyavailable from the Dow Company, Midland, Mich.); and

DMPA is 2,2-dimethylopropionic acid.

The following prepolymer samples were prepared with MDI isomer mixtures,such as Lupranate® MI and Mondur® ML, containing a high level of2,4′-MDI.

Example 1

The preparation of the prepolymer was conducted in a glove box withnitrogen atmosphere. A 2000 ml Pyrex® glass reaction kettle, which wasequipped with an air pressure driven stirrer, a heating mantle, and athermocouple temperature measurement, was charged with about 382.5 gramsof Terathane® 1800 glycol and about 12.5 grams of DMPA. This mixture washeated to about 50° C. with stirring, followed by the addition of about105 grams of Lupranate® MI diisocyanate. The reaction mixture was thenheated to about 90° C. with continuous stirring and held at about 90° C.for about 120 minutes, after which time the reaction was completed, asthe % NCO of the mixture declined to a stable value, matching thecalculated value (% NCO aim of 1.914) of the prepolymer with isocyanateend groups. The viscosity of the prepolymer was determined in accordancewith the general method of ASTM D1343-69 using a Model DV-8 Falling BallViscometer, (sold by Duratech Corp., Waynesboro, Va.), operated at about40° C. The total isocyanate moiety content, in terms of the weightpercent of NCO groups, of the capped glycol prepolymer was measured bythe method of S. Siggia, “Quantitative Organic Analysis via FunctionalGroup”, 3rd Edition, Wiley & Sons, New York, pp. 559–561 (1963), theentire disclosure of which is incorporated herein by reference.

Example 2

The preparation procedures were the same as Example 1, except that thefollowing ingredients were used in the reaction mixture:

-   Terathane® 1800: about 361 grams;-   DMPA: about 19 grams; and-   Mondur® ML: about 120 grams.

Example 3

The preparation procedures were the same as Example 1, except that thefollowing ingredients were used in the reaction mixture:

-   Terathane® 1800: about 349 grams;-   DMPA: about 21 grams; and-   Mondur® ML: about 130 grams.

Example 4

The preparation procedures were the same as Example 1, except that thefollowing ingredients were used in the reaction mixture:

-   Terathane® 1800: about 329 grams;-   Pluracol® HP 4000D: about 30 grams;-   DMPA: about 21 grams; and-   Mondur® ML: 6 about 120 grams.

Example 5

The preparation procedures were the same as Example 1, except that thefollowing ingredients were used in the reaction mixture:

-   Terathane® 1800: about 331 grams;-   Pluracol® HP 4000D: about 30 grams;-   DMPA: about 19 grams; and-   Mondur® ML: about 120 grams.

Comparative Examples

In the following prepolymer samples the preparation procedures and theingredient type and amount were kept the same, except for the MDIdiisocyanate. For comparison, Isonate® 125MDR was used at the sameamount in place of Lupranate® MI or Mondur® ML in the reaction mixturesas shown below:

Example 6C

-   Terathane® 1800: about 382.5 grams;-   DMPA: about 12.5 grams; and-   Isonate® 125MDR: about 105 grams.

Example 7C

-   Terathane® 1800: about 361 grams;-   DMPA: about 19 grams; and-   Isonate® 125MDR: about 120 grams.

Example 8C

-   Terathane® 1800: about 349 grams;-   DMPA: about 21 grams; and-   Isonate® 125MDR: about 130 grams.

Example 9C

-   Terathane® 1800: about 329 grams;-   Pluracol® HP 4000D: about 30 grams;-   DMPA: about 21 grams; and-   Isonate® 125MDR: about 120 grams.

Example 10C

-   Terathane® 1800: about 331 grams;-   Pluracol® HP 4000D: about 30 grams;-   DMPA: about 19 grams; and-   Isonate® 125MDR: about 120 grams.

The viscosities, as measured by the falling ball method at 40° C., ofthe example prepolymer samples, (Examples 1 through 5) and comparativeexamples samples (Examples 6C through 10C) are listed in Table 1 forcomparison:

TABLE 1 Prepolymer viscosities in poises by falling ball method at 40°C. Falling Ball Viscosity at 40° C. Example (poise)  1 3086  2 3292  32468  4 4382  5 3876  6C 6722  7C 7690  8C 6560  9C 12148 10C 6187

As shown in Table 1, the prepolymers prepared with Lupranate® MI orMondur® ML gave substantially lower viscosity, in the absence of anysolvent during or after the prepolymer preparation, than those preparedwith Isonate® 125MDR. The prepolymer viscosities from the comparativeexample samples, without the dilution using a solvent, were too high tobe transported and dispersed in water in downstream processing.

Example 11

The solvent-free prepolymer, as prepared according to the procedures andcomposition described in Example 1, was used to make thepolyurethaneurea aqueous dispersion of the present invention.

A 2,000 ml stainless steel beaker was charged with about 700 grams ofde-ionized water, about 15 grams of sodium dodecylbenzenesulfonate(SDBS), and about 10 grams of triethylamine (TEA). This mixture was thencooled with ice/water to about 5° C. and mixed with a high shearlaboratory mixer with rotor/stator mix head (Ross, Model 100LC) at about5,000 rpm for about 30 seconds. The viscous prepolymer, prepared in themanner as Example 1 and contained in a metal tubular cylinder, was addedto the bottom of the mix head in the aqueous solution through a flexibletubing with applied air pressure. The temperature of the prepolymer wasmaintained between about 50° C. and about 70° C. The extruded prepolymerstream was dispersed and chain-extended with water under the continuousmixing of about 5,000 rpm. In a period of about 50 minutes, a totalamount of about 540 grams of prepolymer was introduced and dispersed inwater. Immediately after the prepolymer was added and dispersed, thedispersed mixture was charged with about 2 grams of Additive 65(commercially available from Dow Corning®, Midland Mich.) and about 6grams of diethylamine (DEA). The reaction mixture was then mixed forabout another 30 minutes. The resulting solvent-free aqueous dispersionwas milky white and stable. The viscosity of the dispersion was adjustedwith the addition and mixing of Hauthane HA thickening agent 900(commercially available from Hauthway, Lynn, Mass.) at a level of about2.0 wt % of the aqueous dispersion. The viscous dispersion was thenfiltered through a 40 micron Bendix metal mesh filter and stored at roomtemperatures for film casting or lamination uses. The dispersion hadsolids level of 43% and a viscosity of about 25,000 centipoises. Thecast film from this dispersion was soft, tacky, and elastomeric.

Example 12

The solvent-free prepolymer, as prepared according to the procedures andcomposition described in Example 1, was used to make thepolyurethaneurea aqueous dispersion of the present invention.

A 2,000 ml stainless steel beaker was charged with about 900 grams ofde-ionized water, about 15 grams of sodium dodecylbenzenesulfonate(SDBS), and about 10 grams of triethylamine (TEA). This mixture was thencooled with ice/water to about 5° C. and mixed with a high shearlaboratory mixer with rotor/stator mix head (Ross, Model 100LC) at about5,000 rpm for about 30 seconds. The viscous prepolymer, prepared in themanner as Example 1 and contained in a metal tubular cylinder, was addedto the bottom of the mix head in the aqueous solution through a flexibletubing with applied air pressure. The temperature of the prepolymer wasmaintained between about 50° C. and about 70° C. The extruded prepolymerstream was dispersed and chain-extended with water under the continuousmixing of about 5,000 rpm. In a period of about 50 minutes, a totalamount of about 540 grams of prepolymer was introduced and dispersed inwater. Immediately after the prepolymer was added and dispersed, thedispersed mixture was charged with about 2 grams of Additive 65(commercially available from Dow Corning®, Midland Mich.) and about 6grams of diethylamine (DEA). The reaction mixture was then mixed forabout another 30 minutes. The resulting solvent-free aqueous dispersionwas milky white and stable. The viscous dispersion was then filteredthrough a 40 micron Bendix metal mesh filter and stored at roomtemperatures for film casting or lamination uses. The dispersion hadsolids level of 40% and a viscosity of about 28 centipoises. The castfilm from this dispersion was soft, tacky, and elastomeric.

Example 13

The solvent-free prepolymer, as prepared according to the procedures andcomposition described in Example 1, was used to make thepolyurethaneurea aqueous dispersion of the present invention.

A 2,000 ml stainless steel beaker was charged with about 700 grams ofde-ionized water, about 15 grams of sodium dodecylbenzenesulfonate(SDBS), and about 10 grams of triethylamine (TEA). This mixture was thencooled with ice/water to about 5° C. and mixed with a high shearlaboratory mixer with rotor/stator mix head (Ross, Model 100LC) at about5,000 rpm for about 30 seconds. The viscous prepolymer, prepared in themanner as Example 1 and contained in a metal tubular cylinder, was addedto the bottom of the mix head in the aqueous solution through a flexibletubing with applied air pressure. The temperature of the prepolymer wasmaintained between about 50° C. and about 70° C. The extruded prepolymerstream was dispersed and chain-extended with water under the continuousmixing of about 5,000 rpm. In a period of about 50 minutes, a totalamount of about 540 grams of prepolymer was introduced and dispersed inwater. Immediately after the prepolymer was added and dispersed, thedispersed mixture was charged with about 2 grams of Additive 65(commercially available from Dow Corning®, Midland Mich.) and about 6grams of diethylamine (DEA). The reaction mixture was then mixed forabout another 30 minutes. The resulting solvent-free aqueous dispersionwas milky white and stable. The viscous dispersion was then filteredthrough a 40 micron Bendix metal mesh filter and stored at roomtemperatures for film casting or lamination uses. The dispersion hadsolids level of 43% and a viscosity of about 28 centipoises. The castfilm from this dispersion was soft, tacky, and elastomeric.

Example 14C

The preparation procedures were the same as Example 11, except that DEAwas not added into the dispersion after the prepolymer was mixed.Initially, the dispersion appeared to be no different from Example 11.However, when the dispersion was aged at room temperatures for one weekor more, the film cast from this dispersion Was brittle and not suitablefor adhesions or laminations.

Example 15

The filtered aqueous dispersion as prepared in Example 11 was used tocoat films on silicone coated release paper, with a continuous 12-inchlaboratory reverse roll coater. The coater was equipped with a 3-zonedrying oven, with the temperature settings at about 60° C., 75° C. and120° C., respectively. The total residence time of drying was about 6minutes. The dried film of about 3-mil thick was wound up at a speed ofabout 2 meters per minute. The elastomeric film 12 was able to peel offfrom the release paper easily and used for bonding fabrics throughlaminations.

Example 16

The filtered aqueous dispersion as prepared in Example 11 was used tocoat films on silicone coated release paper to form elastomeric film 12.Lab samples were prepared manually by securing a 12 inch×12 inch (30cm×30 cm) sheet of double sided silicone release paper (Covermount DSfrom Print Mount Co., Inc 401-232-0096) to a work surface with maskingtape. The aqueous dispersion was poured onto the release paper and castinto a uniform thickness by spreading the dispersion across the releasepaper using a metal knife blade tool, as shown in FIGS. 8 and 9, havinga 6 inch wide gap of 5 mil thickness. Excess solution was blotted with apaper towel. Castings were air-dried overnight under a hood. Theresulting film 12 was easy to peel away from the release paper forfurther use.

Example 17

The film on release paper 12 from Example 15 was placed onto the back ofa 12 inch×12 inch (30 cm×30 cm) warp knit nylon with spandex fabric 14.The fabric/film/release paper sandwich was fed into a Hashima HP-400CBelt Oven Laminator (Hashima Co., Ltd, Gifu-City Japan, 058-245-4501)and laminated at 165° C., with a 20 second residence time and a pressuresetting of P=1, 16, as shown by path 11 a in FIG. 1. The release paperwas removed, leaving film/fabric laminate stretch article 18 a.

TABLE 2 Peel Strength for Film/Fabric Composites in pounds/inch AdhesionPeel Example Strength (lb/in) 18 2.56 19 1.71 20 4.25 21 1.72 25 6.17 265.26 31 4.06

Example 18

The laminated stretch article 18 a was covered with another 12 inch×12inch (30 cm×30 cm) piece of warp knit nylon spandex fabric. Thefabric/film/fabric sandwich was fed into the Hashima laminator andlaminated at 165° C., with a 20 second residence time and a pressuresetting of P=1, to give stretch article 24 a. The peel strength forExample 18 was 2.56 lb/in, see Table 2.

Example 19

Film 12 of Example 15 was laminated to fabric under the same conditionsas Example 17, with the exception that the lamination temperature was120° C. The release paper was removed, leaving a film/fabric laminatestretch article 18 a. The film side of article 18 a was covered withanother 12 inch×12 inch (30 cm×30 cm) layer of warp knit nylon spandexfabric. The fabric/film/fabric sandwich was fed into the Hashimalaminator and laminated at 165° C., with a 20 second residence time anda pressure setting of P=1 to give a stretch article 24 a. The peelstrength for Example 19 was 1.71 lb/in, see Table 2.

Example 20

In this example, two stretch articles of 18 a were layered with the filmsides facing each other. The fabric/film/film/fabric sandwich was fedinto the Hashima laminator and laminated at 165° C. with a 20 secondresidence time and a pressure setting of P=1 to give a stretch article.The peel strength for Example 20 was 4.25 lb/in, see Table 2.

Example 21

Film 12 of Example 15 was carefully removed from release paper andplaced onto a 12 inch×12 inch (30 cm×30 cm) warp knit nylon with spandexfabric 14. Another 12 inch×12 inch (30 cm×30 cm) layer of warp knitnylon spandex fabric was placed onto cast film 20. Thefabric/film/fabric sandwich 20 was fed into the Hashima laminator andlaminated at 165° C., with 20 a second residence time and a pressuresetting of P=1 22 to give a stretch article 24 a. The peel strength forExample 21 was 1.72 lb/in, see Table 2.

Example 22

A second film was carefully removed from release paper and placed on thefabric/film/fabric sandwich 24 a to form article 26. A second 12 inch×12inch (30 cm×30 cm) layer of warp knit nylon spandex fabric was placedonto the second layer of cast film 28. Thefabric/film/fabric/film/fabric sandwich was fed into the Hashimalaminator and laminated at 165° C., with 20 second residence time and apressure setting of P=1 as in 30, to give stretch article 32 a.

Example 23

In this example, a piece of warp knit nylon spandex fabric (1 inch×12inch (2.5 cm×30 cm)) was dipped into high viscosity aqueous dispersion10 b from Example 11 and pulled out, and then the excess was squeezedoff between gloved fingers. The excess was squeezed off a second timebetween gloved fingers to give the dipped, article 34. The coated stripwas hung and allowed to air dry overnight under a hood to give stretcharticle 38 a, path 21 a in FIG. 2.

Example 24

A piece of lightweight nonwoven fabric, deformable in the cross-machinedirection, is soaked into low viscosity aqueous dispersion 10 b,prepared according to the method of Example 12 (40 wt % solids and 28centipoises). The dipped article 34 is allowed to drip to remove excessdispersion liquid, and then is hung for drying in a fume hood forovernight 36 to give stretch article 38 a, path 21 a in FIG. 2.

Example 25

In this example, stretcharticle 38 a from Example 23 was covered with awarp knit nylon spandex fabric (6 inch×12 inch (15 cm×30 cm)) 40. Thelayered article 40 was fed into the Hashima laminator and laminated at165° C., with 20 second residence time and a pressure setting of P=1 asin 42, path 21 b in FIG. 2, to give stretch article 44 a. The peelstrength for Example 25 was 6.17 lb/in, see Table 2.

Example 26

In this example, stretch article 44 a was covered with a warp knit nylonspandex fabric (6 inch×12 inch (15 cm×30 cm)) 46, path 21 c in FIG. 2.The layered article 46 was fed into the Hashima laminator and laminatedat 165° C., with 20 second residence time and a pressure setting of P=1as in 48 to give stretch article 50 a. The peel strength for, Example 26was 5.26 lb/in, see Table 2.

Example 27

In this example, a filtered solution of the aqueous dispersion asprepared in Example 12 is poured into a typical spray bottle. Thefiltered aqueous dispersion 10 c is applied directly to bistretchcotton/spandex twill fabric using spray bottle, 52 as shown in FIG. 3.The fabric is air-dried, 54, to form a stretch article 56 a, path 31 ain FIG. 3.

Example 28

A piece of stretch denim fabric is pretreated by soaking into a bathcontaining a water solution of 20 wt. % calcium nitrate tetrahydrate asa coagulant and dried in an oven at 100° C. for 30 minutes. The aqueousdispersion 10 c, prepared according to the method of Example 12 (40 wt %solids and 28 centipoises) is coated evenly onto the backside of thepretreated fabric with a blade, as shown in FIGS. 8 and 9, having a 5mil gap thickness. The dispersion is coagulated on the surface of thefabric without soaking through. This fabric is then dried 54 in the ovenat 80° C. for 60 minutes to give a stretch article 56 a, path 31 a inFIG. 3.

Example 29

A piece of stretch denim fabric is coated with a high viscositydispersion 10 c of Example 11 (43 wt % solids and 25000 centipoises).This increased viscosity allows the dispersion coated on one side of thefabric without soaking through the fabric 52. The fabric is dried 54 inan oven at 80° C. for 60 minutes 56 a, path 31 a in FIG. 3.

Example 30

A 12 inch×12 inch (30 cm×30 cm) warp knit nylon spandex fabric piece wassecured to the work surface using masking tape (allowing the fabric tobe held under slight tension in the warp direction). The filteredaqueous dispersion 10 c of Example 11 (43 wt % solids and 25000centipoises) was poured onto the fabric 52. This increased viscosityallows the dispersion coated on one side of the fabric without soakingthrough the fabric 52. A uniform thickness of film was made by spreadingthe dispersion across the fabric using the metal tool, shown in FIGS. 8and 9, having a 6 inch wide gap of 10 mil thickness. Excess solution wasblotted with a paper towel. Coated fabric was air-dried overnight undera hood. The article 52 was fed into the Hashima laminator and laminatedat 165° C., with 20 second residence time and a pressure setting of P=1as in 54 to form a stretch article 56 a, path 31 a in FIG. 3.

Example 31

A 12 inch×12 inch (30 cm×30 cm) warp knit nylon spandex fabric piece wassecured to the work surface using masking tape (allowing the fabric tobe held under slight tension in the warp direction). The filteredaqueous dispersion 10 c of Example 11 (43 wt % solids and 25000centipoises) was poured onto the fabric 52. A uniform thickness of filmwas made by spreading the dispersion across the fabric using the metaltool, shown in FIGS. 8 and 9, having a 6 inch wide gap of 10 milthickness. Excess solution was blotted with a paper towel. Another 12inch×12 inch (30 cm×30 cm) warp knit nylon spandex fabric was laid overthe dispersion and lightly pressed to promote adhesion 58, path 31 b inFIG. 3. The coated fabric sandwich was air-dried overnight under a hood.The layered article 58 was fed into the Hashima laminator and laminatedat 165° C., with 20 second residence time and a pressure setting of P=1as in 60 to givestretch article 62 a. The peel strength for Example 31was 4.06 lb/in, see Table 2.

TABLE 3 Molded Bra Cup Height in cm Height Immediately Height AfterAfter Molding 2A Wash Example (cm) Cycle (cm) 32 7.4 4.2 33C 7.3 1.9 346.7 6.4 35C 6.8 5.9

Example 32

Stretch article 24 a, FIG. 1, was made according to Example 21 exceptthat 100% cotton circular knit-fabric was used as the top fabric and thebottom fabric. A 12 inch×12 inch (30 cm×30 cm) piece of cotton basedstretch article 24 a was molded into a bra cup using a TexilformungWilli Lehman GmbH Molding Machine Type 2030 NT equipped with an 8.5 cmdeep circular bullet mold. The bullet and conical mold base were heatedto 195° C., while the ring clamp was heated to 185° C. The fabric wasmolded according to standard practice for 45 seconds. The cup height wasmeasured immediately after molding and again after a wash and dry cycleaccording to AATCC Test Method 150-2001. The laminated and molded cupwith cotton had a height of 7.4 cm. After washing, the cup of Example 32had a height of 4.2 cm.

Example 33C

A 12 inch×12 inch (30 cm×30 cm) piece of 100% cotton circular knit wasmolded in the same manner as Example 32. The cup height was measuredimmediately after molding and again after a wash and dry cycle accordingto AATCC Test Method 150-2001. The 100% cotton circular knit molded cuphad a height of 7.3 cm. After washing the cup of Example 33C had aheight of 1.9 cm.

Example 34

Stretch article 24 a, FIG. 1, was made with warp knit nylon spandexfabric as top fabric and bottom fabric, according to Example 21. A 12inch×12 inch (30 cm×30 cm) piece of warp knit nylon spandex basedstretch article 24 a was molded in the same manner as Example 32. Thecup height was measured immediately after molding and again after a washand dry cycle according to AATCC Test Method 150-2001. The laminated andmolded cup had a height of 6.7 cm. After washing the cup of Example 34had a height of 6.4 cm.

Example 35C

A 12 inch×12 inch (30 cm×30 cm) piece of 100% warp knit nylon was moldedin the same manner as Example 32. The cup height was measuredimmediately after molding and again after a wash and dry cycle accordingto AATCC Test Method 150-2001. The laminated and molded cup had a heightof 6.8 cm. After washing the cup of Example 35C had a height of 5.9 cm.

While the present invention has been described in an illustrativemanner, it should be understood that the terminology used is intended tobe in a nature of words or description rather than of limitation.Furthermore, while the present invention has been described in terms ofseveral illustrative embodiments, it is to be appreciated that thoseskilled in the art will readily apply these teachings to other possiblevariations of the invention.

1. A stretch article comprising: at least one adhesive film or tape of:a substantially solvent-free aqueous polyurethane dispersion of: (1) aprepolymer, which comprises: a) at least one polyether or polyesterpolyol, wherein said polyether or polyester polyol has a number averagemolecular weight of about 600 to about 3,500; b) a mixture of 4,4′-and2,4′-methylene bis(phenyl isocyanate) (MDI) isomers, wherein the ratioof 4,4′-MDI to 2,4′-MDI isomers ranges from about 65:35 to about 35:65;and c) at least one dial compound comprising: hydroxy groups capable ofreacting with the mixture of MDI isomers of component b) and at leastone carboxylic acid group capable of forming a salt upon neutralization,wherein said at least one carboxylic acid group is incapable of reactingwith the mixture of MDI isomers of component b); (2) at least oneneutralizing agent to form an ionic salt with the at least one diolcompound; and (3) at least one monofunctional dialkyl amine compound asa blocking agent for isocyanate groups; and a substrate to which saidadhesive film or tape is applied, wherein the adhesive film or tape isapplied to the substrate upon release from a release paper.
 2. Thestretch article according to claim 1, wherein the adhesive film or tapeis bonded or adhered textile fabric.
 3. The stretch article according toclaim 2, wherein the adhesive film or tape is bonded or adhered to aseam or a support area on the textile fabric.
 4. The stretch articleaccording to claim 2, wherein the article is a garment.
 5. The stretcharticle according to claim 4, wherein the garment is selected from thegroup consisting of undergarments, brassieres, panties, lingerie,swimwear, shapers, camisoles, hosiery, sleepwear, aprons, wetsuits,ties, scrubs, space suits, uniforms, hats, garters, sweatbands, belts,activewear, outerwear, rainwear, cold-weather jackets, pants, shirtings,dresses, blouses, mens and womens tops, and sweaters.
 6. The stretcharticle according to claim 5, wherein the garment is selected from thegroup consisting of undergarments, brassieres, panties, and lingerie.